Copolymers of unsaturated ethers



Patented Aug 1, 1950 COPOLYMERS F UNSATURATED ETHERS Daniel Swern,Philadelphia, Pa., assignor to the United States oi America asrepresented by the Secretary of Agriculture No Drawing. ApplicationJanuary 16, 1948, Serial No. 2,797

13 Claims.

(Granted under the act of March 3, 1883, as

amended April 30, 1928; 370 O. G. 757) This application is made underthe act of March 3, 1883, as amended by the act of April 30, 1928, andthe invention herein described and claimed ii patented in any country,may be manufactured and used by or for the Government of the UnitedStates oi America throughout the World for sovernmental purposes withoutthe payment to me oi any royolty thereon.

This invention relates to plastic compositions. it relates particularlyto eopolymers or oleiluic compounds with unsaturated others derived iromions chain iotty compounds. and has among its ohlects the provision atnew compositions oi matter and processes tor their preparation.

it is moon that a number of long chain compounds derived iroin lots andoils possess properties that render them useiul us softeners andpioeticioine scents. Utilisation oi such com pounds in. the productionoi plastics is often limiteel, however, by their low compatibility withmany high molecular substances. Furthermore, mony oi these plostlcislngagents when incorporated into the polymeric resinous material bymechanical means such as milling, or by forming a solution oi thecomponents, with subsequent elimination oi the solvent. tend to exudefrom the resulting products, thereby imparting an undesirable "greasyfeel" and a foggy appearance to the nlssticised material. These inherentdisadvantages of long chain modifiers and plasticiaing agents can beobviated by the production 01 lntramolecularly plasticized compositions,wherein the plosticislng or mmlifylng agent is chemicclly bound in thepolymer molecule by copolymerizotion with a reactive monomer.Heretotore, one dimculty in making the fatty compound an integral partof the polymer molecule by a copolymerizatlon process has been the lackof suitable fat or oil derivatives containing the necessary functionalgroups.

I have found that compounds corresponding to the general iormula uniom)[IE-Loin (cum-m T t r where R is the radical or an aliphaticmonounsaturated olennic alcohol preferably free of subatituents otherthan halogen and R1 is the primary alcohol group C'H:OH or the estergroup COOR wherein R has the above stated significance, can becopolymerized with oleflnic monomers, thereby modifying thecharacteristics of and imparting desirable properties to the resultin;polymeric material.

iii

ulor polymers.

til

iii

In accordance with the method of my invention a mixture comprising anoleflnio monomer and a compound corresponding to the aforementionedgeneral formula is polymerized by any suitable means such as heat, lightand/or a. catalyst. Preferably, polymerization is eflected by heatingthe monomer mixture at a temperature of about iii" to C. in the presenceof a polymerization catalyst or initiator such as an orsonic peroxidelike benzoyl, lauroyl, stearoyl peroxide; a persuliate like ammoniumpersulfate; or other similar compounds commonly utilized as eatalysticagents in the production of high molec- The polymerization process canbe conducted either by bulls polymerization on the monomer mixture, orby emulsion polymerisation, or in the presence of suitable inertsolvents or diluents.

The method of the present invention is applicable in general, tocopolymerization of olefinio monomers with compounds containing aprimary alcohol croup or an aliphatic, monounsaturated. oleflnlc,carbonyl ester group, linked to a WW- rlihydrorryoctadecyl radicalhaving one of the hydroxyl groups etherifled by an aliphaticmonounsaturated olefinic alcohol. Suitable compounds include, forexample, the unsaturated etheresters oi 9,1il-dihydroxystearic acidsdescribed in my copending application, Serial No. 2,796 filed January16, 1948 and unsaturated. others of 9,1il-dlhydrouyoctadecanol describedin my copending application Serial No. 2,795, filed Janucry 16, 19%, nowU. S. Patent No. 2,491,533. One of several of the aforementioned othersor etheresters can be copolymerized with various active oleilnicmonomers, for example vinyl compounds like vinyl chloride, vinyl acetateor styrene; butadiene, isoprene, unsaturated phthalates like diallylphthalate, acrylonitrile, isobutylene, polymerizable derivatives ofmaleic acid such as diallyl maleate and the like, used either singly orin combination.

The characteristics of the materials thus obtained can be varied by thechoice oi and the relative proportions of the individual componentspresent in the monomer mixture and the conditions of polymerization. Theunsaturated ether-esters of 9,10-dihydroxystearic acid and ethers of9,10-dihydroxyoctadecanol suitable for use in my process may beprepared, for example, by reacting the unsaturated alcohol with 9.10"-epoxystearic acid and 9,10-epoxyoctadecanol, respectively, as describedin my copending applications Serial No. 2,795 and 2,796.

The following Examples I and II describe the 3 preparation ofunsaturated ether-esters of 0, dihydroxystearic acid. Preparation ofunsaturated ethers o! 9,10-dihydroxyoctadecanol is described in Examples111 and IV.

Example I 29.9 g. 9,10-epoxystearic acid were dissolved in 120 ml. ofallyl alcohol, with gentle heating. The solution was cooled below 30 C.and 0.3 g. of 95% sulfuric-acid added with agitation. The

mixture was heated on a steam bath for two.

filtration and discarded, and the solvent was evaporated from thefiltrate. The residual oil consisted of almost pure allyl 9,10(10,9)-alloxyhydroxystearatewhich on redistiliation yielded a product havingthe following characteristics. Boiling range: .l9.6-202 C./ 0.350.5 mm.Saponiflcation equivalent: 387.5 n,,-":1.4589 dz0.9266

Example 11 Beta chloroallyl-Q,10(10,9) -beta-chloroalloxyhydroxystearatewas prepared by reacting 9,10- epoxystearic acid with beta-chloroallylalcohol by the procedure described in Example I and using 4 ml. ofalcohol per gram of epoxystearic acid. Ai'ter separation of theunreacted beta-chloroallyl alcohol by vacuum distillation, the residualreaction product was dissolved in ether and the ether solution waswashed with water until free of sulfuric acid, treated with activatedcarbon for one hour, filteredand the ether evaporated.

The residue .was an amber colored liquid consisting essentially ofbeta-chloroallyl 9,10(10,9) beta-chloroalloxyhydroxystearate.

Example HI 9,10(10,9) -alloxyhydroxyoctadecanol, prepared and isolatedby the procedure described in Example I, using 27.2 grams of9,10-epoxyoctadecanol, 109 ml. of allyl alcohol and 0.3 gram of 95%sulfuric acid, had the following character'- istics:

Boiling range-z 171-188 C./0.02-0.03 mm. Molecular refraction: 102.9 n:1.4627. d4 :0.9166

Example IV 9,10(10,9) beta chloroalloxyhydroxyoctadecanol was preparedby reacting 9,10-epoxyoctadecanol with beta-chloroallyl alcohol by theprocedure described in Example I and using 3 ml. of chloroallyl alcoholper gram of normal epoxyoctadecanol-l.

After neutralization of the catalyst with sodium bicarbonate, theunreacted beta-chloroallyl alcohol was distilled ofi under reducedpressure and the residue was dissolved in acetone (3 ml. per gram) andtreated with activated carbon for one hour; The solution was filtered,cooled to about -.20 C. and the small amount of precipitate which formedwas filtered oil and discarded. The acetone was distilled from thefiltrate yielding as a residue 9,10,(10,9)-beta-chloroalloxyhydroxyoctadeeanol.

The following example illustrates the preparation of copolymers withactive oleflnic monomers.

Example V Mixtures of allyl 9,10( 10,9) -alloxyhydr oxystearate andvinyl acetate, to which. 0.5% by weight of benzoyl peroxide was added,were polymerized by heating first at about 48 to 50 C. for 72 hours,then at about to 75 C. for 48 hours, and finally at about C. for 24hours. The composition of the monomer mixtures used and the physicalproperties of the resulting polymerization products are shown in thefollowing table:

Composition 0! Monomer Mixture an, m by weight) 7 Polymerizate Ally]0,1060 9)- Alloxyhydro'xy- Vinyl Acetate Solubility z stearale o s Hard,1 99 I Do. 9 91 I Do. 2) 80 I Tough, rubbery. 30 70 I Soft, rubbery. 4060 I Do.

: are used in place of the vinyl acetate in the foregoing example. Inplace of allyl-9,10(10,9)- alloxyhydrowstearate there can be used otherunsaturated ether-esters of 9,10-dihydroxystearic acid; for examplethose described in application Serial No. 2,796.

Similar homogeneous products are also found by copolymerizingunsaturated ethers of 9,10 dihydroxy normal octadecanol 1. for example9,10(10,9) -alloxyhydroxyoctadecanol, or 9,10(10,9)-betachloroalloxyhydroxyoctadecanol with vinyl acetate, or with other activeoleflnic monomers, such as those mentioned above, using the proceduredescribed in the foregoing example.

Other organic peroxides and similar polymerization catalysts such'as'persulfates and the like can be used in place of benzoyl peroxide.Polymerization can be conducted by maintaining the monomer mixture atany temperature within the range of about 40 to 100 C. for a suiiicientlength of time; the rate of polymerization increasing with thetemperature.

The designation 9,10('10,9) signifies that the product consists of a.mixture of the 9,10 and 10,9 comopunds, formed as illustrated on page 1of each application, Serial No. 2,795 and Serial No. 2,796. Thenomenclature is in accordance with generally accepted usage; see J. Am.Chem. m. 70, 1226,1235 et seq. (1948).

The expression, the radical of an aliphatic monounsaturted oleflnicalcohol, is employed in its usual sense, the radical being the partremaining after subtracting the alcoholic OH group.

Having thus described my invention, I claim:

1. A process comprising conjointly polymerizing-a monomericpolymerizable oleflnic compound witha compound corresponding to thegeneral wherein R is the radical ct an aliphatic monounsaturatedoleflnic alcohol and R1 is a member of the group consisting of --CH2OHand -COOR the R redicals being identical. by heating at about 40 to 100C. in the presence of a polymerization catalyst taken from the groupconsisting of organic peroxides and inorganic persulfates.

2. The process comprising conjointly polymerizing vinyl acetate with acompound of the general formula [Ht-H] 1 cnii1ciooa Ln -0RJ l where R isthe radical of an allyl alcohol taken from the group consisting of allylalcohol and a chloroallyl alcohol, at about 40 to 100 C.

3. The process of claim 2 wherein R is the radical of a monochlorallylalcohol.

4. The process of claim 2 wherein R is CH2=CH-CH2- 5. The process ofclaim 2 wherein R is cHi=cc1-cH2- 6. The copolymer of a monomericolymerizable oleflnic compound with a compound corresponding to thegeneral formula ratwherein R is the radical of an aliphaticmonounsaturated olefinic alcohol and R1 is a member of the groupconsisting of CH:0H and CO0R, the R radicals being identical.

7. The copolymer of vinyl acetate with an allyl ester-mono allyl etherof 9,10-dihydroxystearic acid. v

8. The coplymer of vinyl acetate with a monoallyl ether of9,10-dihydroxy-normal octadecanol- 1, the allyl radical being in one ofthe 9 and 10 positions.

9. The process of claim 1 in which the weight ratio of the saidmonomeric polymerizable oleflmc compound to the compound of the recitedgeneral formula is in the range from 99 to 1, to 60 to 40.

10. The process of claim 2 in which the weight ratio of the vinylacetate to the compound of the recited general formula is in the rangefrom 99 to 1, to 60 to 40.

11. The copolymer of vinyl acetate with allyl ester-mono allyl ether of9,10-dihydr0xystearic acid, the weight ratio of the vinyl acetate to thelatter being in the range from 99 to 1, to 60 to 40.

12. A process comprising conjointly polymerizing a monomericpolymerizable vinyl ester with REFERENCES CITED The following referencesare of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,437,508 DAlelio Mar. 9, 19482,440,237 Adelson et al. Apr. 27, 1948 40 2,448,246 Barker et a1 Aug.31, 1948

6. THE COPOLYMER OF A MONOMERIC POLYMERIZABLE OLEFINIC COMPOUND WITH ACOMPOUND CORRESPONDING TO THE GENERAL FORMULA